CN114917521B - Temperature response type double-shell microcapsule fire extinguishing agent and preparation method thereof - Google Patents
Temperature response type double-shell microcapsule fire extinguishing agent and preparation method thereof Download PDFInfo
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- CN114917521B CN114917521B CN202210537803.5A CN202210537803A CN114917521B CN 114917521 B CN114917521 B CN 114917521B CN 202210537803 A CN202210537803 A CN 202210537803A CN 114917521 B CN114917521 B CN 114917521B
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- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D1/00—Fire-extinguishing compositions; Use of chemical substances in extinguishing fires
- A62D1/0007—Solid extinguishing substances
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Abstract
The invention discloses a temperature response type double-shell microcapsule fire extinguishing agent and a preparation method thereof. The double-shell microcapsule fire extinguishing agent comprises a core body, a first shell and a second shell, wherein the first shell is coated outside the core body, and the second shell is coated outside the first shell; the core body is a liquid fire extinguishing agent and is selected from one or a mixture of more of perfluorohexanone, heptafluorocyclopentane, bromotrifluoropropene, tetrafluorodibromoethane, trifluorodichloroethane and dibromomethane; the first shell is made of a mixture of hexamethylene diamine and sebacoyl chloride or a mixture of hexamethylene diamine and adipic acid; the second shell is made of epoxy resin ED-20 or alkyd resin. The microcapsule fire extinguishing agent provided by the invention can respond to the change of the environmental temperature, and achieves the purposes of automatic starting and automatic fire extinguishing. When the ambient temperature reaches 120-250 ℃, the shell of the microcapsule is broken, and the fire extinguishing agent can be released.
Description
Technical Field
The invention belongs to the technical field of fire extinguishing agents, and particularly relates to a temperature response type double-shell microcapsule fire extinguishing agent and a preparation method thereof.
Background
Today, with the development of technology, fire is still a common emergency disaster. The fire disaster not only causes a great amount of financial loss and deprives people of health and life, but also causes environmental pollution and damage to ecological balance, and indirectly threatens human survival. Therefore, fire prevention and extinguishment remain the subject of considerable contemporary life. The development and development of the fire extinguishing agent can effectively prevent and control fire, protect the life safety of people and reduce property loss caused by the fire. Most of the fire extinguishing agents at present have the problems of complicated required equipment, strict technical requirements, high spraying pressure, inconvenient storage, movement and carrying, and the like when in use, and the use is limited.
The microencapsulation of the fire extinguishing agent to form the microcapsule fire extinguishing agent is an important means for solving the problems existing in the common fire extinguishing agent. Patent CN113230577A discloses a preparation method of a microcapsule fire extinguishing agent using urea resin as a wall material, which takes melamine, urea and formaldehyde as monomers to react at 70 ℃ to generate a resin-coated low-boiling-point fire extinguishing agent; the disadvantage is that the reaction temperature is higher than the boiling point of the fire extinguishing agent, which causes the loss of core materials. The patent RU2899168A discloses a preparation method of a microcapsule of a double-layer coated halogenated hydrocarbon fire extinguishing agent, wherein a gelatin modified amino resin composite material is used as a first layer of capsule wall, an acrylate polymer is used as a second layer of capsule wall, and a graft transition region is formed between the first layer of capsule wall and the second layer of capsule wall through graft copolymerization of gelatin and acrylate; although the core of the microcapsule prepared by the method can extinguish fire, the shell layer does not have the function of flame retardance. Patent RU2015133303A discloses a preparation method of a fire extinguishing agent, gelatin is used as a first shell, resorcinol and formaldehyde are used as a second shell, and microcapsules prepared by the method have a fire extinguishing effect, but the shell materials are not environment-friendly, and harmful gases are generated when the shell materials meet high temperature.
Therefore, the development of an environment-friendly high-efficiency microcapsule fire extinguishing agent with double functions of fire retardation and fire extinguishing has important significance in extinguishing fire.
Disclosure of Invention
To is directed at
The reaction temperature is higher than the boiling point of the core material, so that the extinguishing agent is volatilized and lost;
the core of the microcapsule can extinguish fire, but the shell material does not have the function of flame retardance;
the invention provides a temperature response type double-shell microcapsule fire extinguishing agent and a preparation method thereof, and solves the technical problems that an encapsulation material is not environment-friendly and generates harmful substances to the environment when being heated.
In order to achieve the purpose, the invention adopts the following technical scheme:
a double-shell microcapsule fire extinguishing agent comprises a core body, a first shell and a second shell, wherein the first shell is coated outside the core body, and the second shell is coated outside the first shell;
the core body is a liquid fire extinguishing agent and is selected from one or a mixture of more of perfluorohexanone, heptafluorocyclopentane, bromotrifluoropropene, tetrafluorodibromoethane, trifluorodichloroethane and dibromomethane;
the first shell is made of hexamethylenediamine and sebacoyl chloride or hexamethylenediamine and adipic acid;
the second shell is made of epoxy resin ED-20 or alkyd resin.
The preparation method of the double-shell microcapsule fire extinguishing agent comprises the following steps:
(1) Preparing a wall material solution: adding the first layer of shell into deionized water to obtain an aqueous solution; diluting the second shell with a diluent to obtain a resin solution;
(2) Emulsification: adding a liquid fire extinguishing agent into the aqueous solution of the first layer of shell, adding an emulsifier, and stirring at a high speed to form a stable emulsion;
(3) Formation of the first shell: adding an acidic substance into the emulsion to adjust the pH value of the solution to 3-6, slowly heating the system temperature to 30 ℃ at the speed of 800r/min, and reacting for 1h to obtain a single-layer microcapsule fire extinguishing agent;
(4) Forming a second layer shell: filtering the single-layer microcapsule fire extinguishing agent, adding the filtered single-layer microcapsule fire extinguishing agent into a resin solution, stirring and mixing uniformly, reducing the temperature of the system to 20 ℃, adding a curing agent for curing reaction to form double-shell microcapsules;
(5) And (3) drying: and filtering the double-shell microcapsule, and freeze-drying to obtain solid microcapsule powder.
Preferably, the method comprises the following steps:
in the step (1), the mass concentrations of the aqueous solution of hexamethylene diamine, the aqueous solution of sebacoyl chloride and the aqueous solution of adipic acid are all 2-5%.
In the step (1), the diluent is selected from polyglycidyl ether, propylene oxide butyl ether, propylene oxide phenyl ether, propylene oxide ethyl ether or propylene oxide propyl ether.
In the step (1), the volume ratio of the diluent to the second shell is 4 to 8.
In the step (2), the mass ratio of the liquid fire extinguishing agent to the first shell is 1-4.
In the step (2), the emulsifier is one or a mixture of several selected from alkylphenol ethoxylates, sodium dodecyl sulfate, polyvinyl alcohol, polystyrene-maleic anhydride copolymer, span80 and Tween20, and the dosage of the emulsifier is 3-8% of the volume of the liquid fire extinguishing agent.
In the step (2), the high-speed stirring speed is 4000 to 8000r/min.
In the step (3), the acidic substance is carbonic acid, acetic acid, potassium hydrogen phthalate, hydrochloric acid or sulfuric acid, and the concentration of the acidic substance is 10%.
In the step (4), the curing agent is ethylenediamine, glutaraldehyde, polyethylene polyamine, dimethylpropylamine or dicyandiamide, and the dosage of the curing agent is 5-8% of the mass of the epoxy resin.
Compared with the prior art, the invention has the following beneficial effects:
according to the microcapsule fire extinguishing agent, hexamethylenediamine and sebacoyl chloride (or hexamethylenediamine and adipic acid) are selected as reaction monomers to generate the first layer of shell, the shell has a good flame retardant effect and good thermal stability, no toxic or harmful substance is generated by decomposition at high temperature, and the microcapsule fire extinguishing agent belongs to an environment-friendly packaging material. And the reaction speed of the hexamethylene diamine and the sebacoyl chloride (or the hexamethylene diamine and the adipic acid) on a two-phase interface is high, and the reaction rate constant reaches 10 2 -10 6 dm 3 And/or the two can react at normal temperature, so that the loss of the volatile fire extinguishing core material can be greatly avoided, and the encapsulation efficiency is improved.
The microcapsule fire extinguishing agent disclosed by the invention is coated by the double-shell coating fire extinguishing agent, so that the compactness of a shell layer can be effectively improved, the mechanical strength of the microcapsule is increased, and the microcapsule fire extinguishing agent can be stored for a long time. And the second shell epoxy resin ED-20 (or alkyd resin) also belongs to an environment-friendly material and has good film-forming property. Under the condition that the microcapsules are not dried, the characteristic of high viscosity of the epoxy resin can be utilized, the wet-sample microcapsules can be directly coated on places needing to prevent fire, and other binder components are not required to be added.
The microcapsule fire extinguishing agent provided by the invention can respond to the change of the environmental temperature, and achieves the purposes of automatic starting and automatic fire extinguishing. When the ambient temperature reaches 120-250 ℃, the shell of the microcapsule is broken, and the fire extinguishing agent can be released.
The microcapsule fire extinguishing agent provided by the invention can effectively extinguish open fire within 8-10s through fire extinguishing performance tests, and does not re-ignite any more, so that the fire extinguishing efficiency is higher.
The microcapsule fire extinguishing agent provided by the invention can be made into products such as patches, coatings and the like according to actual requirements, is applied to machine rooms, transformer boxes and batteries, is small and flexible to use, and is very convenient.
Drawings
FIG. 1 is an optical microscope photograph of the emulsion prepared in example 1.
FIG. 2 is an optical microscope photograph of fire extinguishing agent microcapsules prepared in example 1.
FIG. 3 is a thermogram of a fire extinguishing agent microcapsule prepared in example 1.
Detailed Description
The invention is described in further detail below with reference to the figures and the specific examples, which should not be construed as limiting the invention. Modifications or substitutions to methods, procedures, or conditions of the invention may be made without departing from the spirit and scope of the invention. The experimental methods and reagents of the formulations not specified in the examples are in accordance with the conventional conditions in the art.
Example 1
A preparation method of a temperature response type double-shell microcapsule fire extinguishing agent comprises the following steps:
(1) Preparing a wall material solution: respectively taking a certain amount of hexamethylenediamine and sebacoyl chloride to prepare a hexamethylenediamine solution and a sebacoyl chloride solution with the mass concentration of 3% by 30mL respectively; 2mL of epoxypropane butyl ether is taken to dilute 0.5mL of epoxy resin ED-20 to obtain epoxy resin ED-20 solution.
(2) Emulsification: and (3) adding 5mL of perfluorohexanone into the mixed solution of the hexamethylene diamine solution and the sebacoyl chloride solution, adding 0.18mL of alkylphenol polyoxyethylene, and emulsifying at the rotating speed of 6000r/min for 10min to obtain uniform emulsion.
(3) Formation of the first layer of the shell: and adding 10% of potassium hydrogen phthalate solution into the emulsion to adjust the pH value to 4.0, slowly raising the temperature of the system to 30 ℃, and reacting for 1h at the rotating speed of 2000r/min to obtain the microcapsule fire extinguishing agent coated by the first layer of shell.
(4) Forming a second layer shell: and (2) filtering the microcapsules, adding the microcapsules into the diluted epoxy resin ED-20 solution, keeping the temperature of the system at 20 ℃, keeping the rotating speed at 800r/min, uniformly mixing the microcapsules and the resin, adding a curing agent ethylenediamine, and curing for 30min to obtain the double-shell microcapsule fire extinguishing agent taking the perfluorohexanone as the core material.
(5) And (3) drying: filtering the microcapsule, and freeze drying to obtain solid microcapsule powder.
As shown in the emulsion optical microscope image of FIG. 1, the emulsifier selected in the preparation process can well emulsify the fire extinguishing agent core material, so that the fire extinguishing agent droplets are uniformly dispersed in the water phase.
As shown in the optical microscope image of the fire extinguishing agent microcapsule in figure 2, the prepared microcapsule fire extinguishing agent is in a regular spherical shape, and the particle size is 4-10um.
From the thermogravimetry chart of the fire extinguishing agent microcapsule of fig. 3, the release temperature of the fire extinguishing agent of the prepared microcapsule fire extinguishing agent is about 300 ℃.
Example 2
A preparation method of a temperature response type double-shell microcapsule fire extinguishing agent comprises the following steps:
(1) Preparing a wall material solution: respectively taking a certain amount of hexamethylenediamine and adipic acid to prepare a hexamethylenediamine solution and an adipic acid solution with mass concentration of 2% by 30mL respectively; 4mL of trimethylolpropane propyl ether is taken to dilute 0.5mL of epoxy resin ED-20 to obtain epoxy resin ED-20 solution.
(2) Emulsification: adding 5mL of bromotrifluoropropene into a mixed solution of a hexamethylenediamine solution and a sebacoyl chloride solution, adding 0.2g of sodium dodecyl sulfate, and emulsifying at the rotating speed of 8000r/min for 10min to obtain a uniform emulsion.
(3) Formation of the first shell: and adding 10% acetic acid solution into the emulsion to adjust the pH value to 4.0, slowly raising the temperature of the system to 30 ℃, and reacting for 1h at the rotating speed of 3000r/min to obtain the microcapsule fire extinguishing agent coated by the first layer of shell.
(4) Forming a second layer shell: and (2) filtering the microcapsules, adding the microcapsules into the diluted epoxy resin ED-20 solution, keeping the temperature of the system at 20 ℃, rotating at the speed of 800r/min, uniformly mixing the microcapsules and the resin, adding glutaraldehyde serving as a curing agent, and curing for 30min to obtain the double-shell microcapsule fire extinguishing agent taking bromotrifluoropropene as a core material.
(5) And (3) drying: filtering the microcapsule, and freeze drying to obtain solid microcapsule powder.
Example 3
The same as example 1 except that:
in the step (1), the mass concentration of the hexamethylene diamine solution and the sebacoyl chloride solution is 5%, and the dosage of the diluent epoxypropane butyl ether is 3mL.
In the step (2), the fire extinguishing agent is tetrafluorodibromoethane, the using amount of the emulsifier is 0.3g, and the emulsifying time is 30min.
In the step (3), the pH value of the system is 5, and the reaction time is 2h.
Example 4
The same as example 1 except that:
in the step (2), the fire extinguishing agent is a mixture of perfluorohexanone and tetrafluorodibromoethane, the mixing ratio is 1.
In the step (4), the curing agent is polyethylene polyamine, and the curing time is 1h.
Example 5
The same as example 2 except that:
in the step (1), the mass concentration of the hexamethylene diamine solution and the adipic acid solution is 2%, the resin is alkyd resin, and the diluent is polyglycidyl ether.
In the step (2), the fire extinguishing agent is heptafluorocyclopentane, the emulsifier is polyvinyl alcohol, and the emulsifying time is 20min.
In the step (4), the curing agent is methylpropylamine, the curing temperature is 5 to 10 ℃, and the curing time is 1h.
Claims (8)
1. A double-shell microcapsule fire extinguishing agent is characterized in that: the core body is coated with the first layer of shell, and the second layer of shell is coated with the first layer of shell;
the core body is a liquid fire extinguishing agent and is selected from one or a mixture of more of perfluorohexanone, heptafluorocyclopentane, bromotrifluoropropene, tetrafluorodibromoethane, trifluorodichloroethane and dibromomethane;
the first shell is made of a mixture of hexamethylene diamine and sebacoyl chloride or a mixture of hexamethylene diamine and adipic acid;
the second shell is made of epoxy resin ED-20 or alkyd resin;
the preparation method of the double-shell microcapsule fire extinguishing agent comprises the following steps:
(1) Preparing a wall material solution: adding the first layer of shell into deionized water to obtain an aqueous solution; diluting the second shell with a diluent to obtain a resin solution;
(2) Emulsification: adding a liquid fire extinguishing agent into the aqueous solution of the first layer of shell, adding an emulsifier, and stirring at a high speed to form a stable emulsion;
(3) Formation of the first shell: adding an acidic substance into the emulsion to adjust the pH value of the solution to 3-6, slowly heating the system temperature to 30 ℃ at the speed of 800r/min, and reacting for 1h to obtain a single-layer microcapsule fire extinguishing agent;
(4) Forming a second layer shell: filtering the single-layer microcapsule fire extinguishing agent, adding the filtered single-layer microcapsule fire extinguishing agent into a resin solution, stirring and mixing uniformly, reducing the temperature of the system to 20 ℃, adding a curing agent for curing reaction to form double-shell microcapsules;
(5) And (3) drying: and filtering the double-shell microcapsule, and freeze-drying to obtain solid microcapsule powder.
2. The double-shell microcapsule fire extinguishing agent according to claim 1, wherein: in the step (1), the mass concentration of the aqueous solution of hexamethylene diamine, the aqueous solution of sebacoyl chloride and the aqueous solution of adipic acid is 2-5%.
3. The double-shell microcapsule fire extinguishing agent according to claim 1, wherein: in the step (1), the diluent is selected from polyglycidyl ether, propylene oxide butyl ether, propylene oxide phenyl ether, propylene oxide ethyl ether or propylene oxide propyl ether; the volume ratio of the diluent to the epoxy resin is 4 to 8.
4. The double-shell microcapsule fire extinguishing agent according to claim 1, wherein: in the step (2), the mass ratio of the liquid fire extinguishing agent to the first shell is 1-4.
5. The double-shell microcapsule fire extinguishing agent according to claim 1, wherein: in the step (2), the emulsifier is one or a mixture of several selected from alkylphenol ethoxylates, sodium dodecyl sulfate, polyvinyl alcohol, polystyrene-maleic anhydride copolymer, span80 and Tween20, and the dosage of the emulsifier is 3-8% of the volume of the liquid fire extinguishing agent.
6. The double-shell microcapsule fire extinguishing agent according to claim 1, characterized in that: in the step (2), the high-speed stirring speed is 4000 to 8000r/min.
7. The double-shell microcapsule fire extinguishing agent according to claim 1, wherein: in the step (3), the acidic substance is carbonic acid, acetic acid, potassium hydrogen phthalate, hydrochloric acid or sulfuric acid, and the mass concentration of the acidic substance is 10%.
8. The double-shell microcapsule fire extinguishing agent according to claim 1, wherein: in the step (4), the curing agent is ethylenediamine, glutaraldehyde, polyethylene polyamine, dimethylpropylamine or dicyandiamide, and the dosage of the curing agent is 5-8% of the mass of the epoxy resin.
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| KR20240078516A (en) * | 2022-11-25 | 2024-06-04 | (주)이유씨엔씨 | Fire extinguishing paint composition for early fire extinguishing in utility-pipe conduit local equipment |
| CN116115947A (en) * | 2022-12-13 | 2023-05-16 | 南京理工大学 | Multi-wall microcapsule perfluoro-hexanone fire extinguishing agent and preparation method thereof |
| CN116077881B (en) * | 2023-02-13 | 2024-07-19 | 哲弗智能***（上海）有限公司 | Lithium battery composite coating fire extinguishing agent and preparation method thereof |
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| KR101184790B1 (en) * | 2011-02-10 | 2012-09-20 | 제이에스씨 파이로 치미카 | Standalone Means for Firefighting |
| WO2016089240A1 (en) * | 2014-12-04 | 2016-06-09 | Общество С Ограниченной Ответственностью "Делси" | Microcapsules, method for producing thereof and flame retardant agents, materials, coatings and products based thereon |
| CN109420281A (en) * | 2017-09-04 | 2019-03-05 | 西安威西特消防科技有限责任公司 | A kind of microcapsules self-extinguishing agent |
| KR102237294B1 (en) * | 2019-06-26 | 2021-04-07 | (주)수 | Two-part epoxy paint composition for initial fire suppression using capsule-type fire extinguishing agent and aerosol-type epoxy paint composition |
| CN112043994B (en) * | 2020-09-14 | 2022-03-22 | 西安尚泰安全技术有限责任公司 | Temperature-control capsule type nano fire extinguishing tablet and temperature-control nano capsule fire extinguishing method |
| CN112090016A (en) * | 2020-09-24 | 2020-12-18 | 西安天河矿业科技有限责任公司 | High-water-content capsule fire prevention and extinguishing agent and application thereof |
| KR102328735B1 (en) * | 2020-10-26 | 2021-11-22 | 주식회사 지에프아이 | Microcapsules for fire extinguishing with double layered structure |
| CN113476778B (en) * | 2021-06-21 | 2022-04-15 | 广州十克拉投资有限公司 | High-stability fire-extinguishing microcapsule and preparation method thereof |
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